Vibrational frequencies and intramolecular force constants for cisplatin: assessing the role of the platinum basis set and relativistic effects

被引：8

作者：

de Almeida, Caroline A. ^{[1
]}

Pinto, Larissa P. N. M. ^{[1
]}

Dos Santos, Helio F. ^{[2
]}

Paschoal, Diego F. S. ^{[1
]}

机构：

[1] Univ Fed Rio de Janeiro, Ctr Multidisciplinar UFRJ Macae, Inst Multidisciplinar Quim, NQTCM Nucleo Quim Teor & Computac Macae, BR-27973545 Macae, RJ, Brazil

[2] Univ Fed Juiz De Fora, Dept Quim ICE, NEQC Nucleo Estudos Quim Computac, Dept Quim ICE, Campus Univ, BR-36036900 Juiz De Fora, MG, Brazil

来源：

JOURNAL OF MOLECULAR MODELING | 2021年 / 27卷 / 11期

关键词：

Cisplatin; Vibrational frequencies; Raman; Force constants; Basis set; Relativistic effects; DENSITY-FUNCTIONAL METHODS; EFFECTIVE CORE POTENTIALS; ZETA VALENCE QUALITY; MOLECULAR-MECHANISMS; SPECTRA; ENERGY; DFT; REACTIVITY; PARAMETERS; COMPLEXES;

D O I：

10.1007/s00894-021-04937-4

中图分类号：

Q5 [生物化学]; Q7 [分子生物学];

学科分类号：

071010 ; 081704 ;

摘要：

The role of platinum basis set (PTBS) and relativistic effects for predicting the vibrational frequencies and intramolecular force constants for cisplatin are discussed. Nonrelativistic and relativistic computational protocols were built at B3LYP/PTBS/jorge-DZP/C-PCM and B3LYP-DKH2/PTBS/jorge-DZP-DKH/C-PCM levels, respectively, where 19 distinct PTBS were tested. As expected, the structural parameters were not very sensitive to the PTBS, however, the inclusion of relativistic effects improves the description of the cisplatin structure. When it comes to the vibrational frequencies, the results show that the PTBS, and mainly the relativistic effects, are both important. Moreover, the PBE0 functional led to better results than B3LYP in the protocols PBE0/LANL2TZ(f)/jorge-DZP/C-PCM (P20) and PBE0-DKH2/Sapporo-DKH3-DZP-2012/jorge-DZP-DKH/C-PCM (P22), which provided a mean absolute deviation (MAD) of only 10.8 cm(-1) and 9.5 cm(-1), respectively, for vibrational frequencies, which are excellent choices to study Pt complexes. Finally, a discussion of the intramolecular force constants for cisplatin is carried out, with the calculated bond and angles force constants with P20 and P22 protocols being recommended for the parameterization of the force field of cisplatin.

引用

页数：13